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The large Weilasituo Sn-polymetallic deposit is a recent exploration discovery in the southern Great Xing’an Range, northeast China. The ore cluster area shows horizontal mineralization zoning, from the inner granite body outward, consisting of high- T Sn–W–Li mineralization, middle- T Cu–Zn mineralization and peripheral low- T Pb–Zn–Ag mineralization. However, the intrinsic genetic relationship between Sn-W-Li mineralization and peripheral vein-type Pb–Zn–Ag–Cu mineralization, the formation mechanism and the deep geological background are still insufficiently understood. Here, we use fluid inclusions, trace elements concentrations in quartz and sphalerite, and H–O isotope studies to determine the genetic mechanism and establish a metallogenic model. Fluid inclusion microthermometry and Laser Raman spectroscopic analysis results demonstrates that the aqueous ore-forming fluids evolved from low-medium salinity, medium–high temperature to low salinity, low-medium temperature fluids. Laser Raman spectroscopic analysis shows that CH 4 is ubiquitous in fluid inclusions of all ore stages. Early ore fluids have δ 18 O H2O (v–SMOW) values from + 5.5 to + 6.2‰ and δD values of approximately − 67‰, concordant with a magmatic origin. However, the late ore fluids shifted toward lower δ 18 O H2O (v–SMOW) (as low as 0.3‰) and δD values (~ − 136‰), suggesting mixing between external fluids derived from the wall rocks and a contribution from meteoric water. Ti-in-quartz thermometry indicates a magmatic crystallization temperature of around 700 °C at a pressure of 1.5 kbar for the magmatic ore stage. Cathodoluminescence (CL) imaging and trace element analysis of quartz from a hydrothermal vug highlight at least three growth episodes that relate to different fluid pulses; each episode begins with CL-bright, Al-Li-rich quartz, and ends with CL-dark quartz with low Al and Li contents. Quartz from Episode 1 formed from early Sn-(Zn)-rich fluids which were likely derived from the quartz porphyry. Quartz from episodes 2 and 3 formed from Zn-(Sn)-Cu-rich fluid. The early magmatic fluid is characterized by low f S 2 . The SO 2 produced by magma degassing reacted with heated water to form SO 4 2− , causing the shift from low f S 2 to high f S 2 . The SO 4 2− generated was converted to S 2– by mixing with CH 4 -rich, Fe and Zn-bearing external fluid which led to late-stage alteration and dissolution of micas in vein walls, thus promoting crystallization of pyrrhotite, Fe-rich sphalerite and chalcopyrite and inhibiting the precipitation of anhydrite. This study shows that ore formation encompassed multiple episodes involving steadily evolved fluids, and that the addition of external fluids plays an important role in the formation of the later Cu–Zn and Ag–Pb–Zn mineralization in the Weilasituo ore district.

The Niujiaotang zinc deposit in southeastern Guizhou, China, is a Mississippi Valley-type Zn deposit within Early Cambrian carbonate rocks. Sphalerite is enriched in cadmium (average 1.4 wt.% Cd), which occurs mostly as isomorphous impurities in the sphalerite lattice. Discrete cadmium minerals (greenockite and otavite) are rare and are found almost exclusively in the oxidation zone of the deposit, probably formed as secondary minerals during weathering–leaching processes. Geochemical data show that the sulfides are enriched in heavy sulfur, with δ 34 S ranging from +10.0‰ to +32.8‰ (mean +22.5‰). The consistent Pb isotopic compositions in different sulfide minerals are similar to that of Cambrian strata. The ore lead probably came from U- and Th-rich upper crustal rocks, such as the Lower Cambrian Wuxun Formation. The ore fluid is of low-temperature (101°C to 142°C) type, with a Na–Ca–Mg–Cl-dominant composition, and is interpreted as oil-field brine. The data indicate that the metals were mainly derived from the Early Cambrian strata (Qingxudong and Wuxun Formations), whereas sulfur is sourced from sulfate in Cambrian strata or oil-field brines of the Majiang petroleum paleoreservoir. The genetic model for the deposit invokes an Early Cambrian shallow-sea environment on the Yangtze Platform. Zinc and Cd in seawater were concentrated in abundant algae via unknown biological mechanisms, resulting in large amounts of Zn- and Cd-rich algal ooliths. During the Ordovician, concurrent with destruction of the Majiang petroleum paleoreservoir, oil-field brines migrated from the center of the basin to the margin leaching metals from the Cambrian strata. In the Niujiaotang area, preexisting Zn and Cd, particularly in the Qingxudong and Wuxun Formation, were further mobilized by hot brines rising along the Zaolou fault system, forming stratiform and generally conformable Zn–Cd orebodies in reactive carbonate lithologies.

Laser ablation-inductively coupled plasma-mass spectrometry and electron-probe microanalysis were used to investigate the trace-element contents of sphalerite, chalcopyrite and pyrite from the Plaka Pb–Zn–Ag deposit. Using petrographic observations, the analytical results could be linked to the temporal evolution of the Plaka ore-forming system. Sphalerite chemistry reliably records the temperature and fS2 evolution of the system, with estimated formation temperatures reproducing the microthermometric results from previous fluid-inclusion studies. Chalcopyrite chemistry also shows systematic variations over time, particularly for Cd, Co, Ge, In, Sn and Zn concentrations. Measurable pyrite was only found in association with early high-temperature mineralisation, and no clear trends could therefore be identified. We note, however, that As and Se contents in pyrite are consistent with formation temperatures estimated from co-existing sphalerite. Statistical analysis of the sphalerite data allowed us to identify the dominant geological controls on its trace-element content. The three investigated factors temperature, fS2, and sample location account for > 80% of the observed variance in Mn, Fe, Co, Ga, Ge, In, Sb and Hg concentrations, and > 60% of the observed variance in Cd and Sn concentrations. Only for Cu and Ag concentrations is the explained variance < 50%. A similarly detailed analysis was not possible for chalcopyrite and pyrite. Nevertheless, comparison of the results for all three investigated minerals indicates that there are some systematic variations across the deposit which may be explained by local differences in fluid composition.

Economic interest in indium (In) and other critical metals has accelerated efforts to understand how such elements occur in nature and the controls on their mineralogy. In this contribution, the distribution of In and other trace elements in the Dulong Zn–Sn–In deposit, China, is described, using a holistic approach which targets not only sulfides but also the potential for In and Sn within co-existing oxides and skarn silicates. Sphalerite is the most significant In carrier. Four distinct types of sphalerite are identified, which differ with respect to ore texture and the concentration of In (0.74–4572 ppm). Subordinate amounts of In also occur within chalcopyrite and within andradite garnet, an abundant mineral in the skarn at Dulong and possibly accounting for a significant proportion of total In. Tin is not especially concentrated in either sphalerite or chalcopyrite, occurring instead as cassiterite but with measurable concentrations also in magnetite and skarn silicates. The study confirms that the dominant substitution for In in sphalerite is 2Zn2+ ↔ Cu+ + In3+ but that Ag and Sn may also play a subordinate role in some sphalerite sub-types via the substitution: 3Zn2+ ↔ Ag+ + Sn2+ + In3+. The study highlights that concentrations of In in sphalerite are likely to be heterogeneous at scales from single mineral grains to that of the deposit. The observed partitioning of both In and Sn into skarn silicates, and to a lesser extent, oxides, is a critical factor that may significantly compromise estimations of by-product elements that would be economically recoverable during exploitation of sulfide ores.

The Bianjiadayuan Ag-Pb-Zn deposit (4.81 Mt. @157.4 g/t Ag and 3.94% Pb + Zn) is located in the Great Hinggan Range Pb-Zn-Ag-Cu-Mo-Sn-Fe polymetallic metallogenic belt, NE China. Vein type Pb-Zn-Ag ore bodies are primarily hosted by slate, adjacent to a Sn ± Cu ± Mo mineralized porphyry intrusion. The deposit is characterized by silver-rich ores with Ag grades up to 3000 g/t. Four primary paragenetic sequences are recognized: (I) arsenopyrite + pyrite + quartz, (II) main sulfide + quartz, (III) silver-bearing sulfosalt + quartz, and (IV) boulangerite + calcite. A subsequent supergene oxidation stage has also been identified. Hydrothermal alteration consists of an early episode of silicification, two intermediate episodes (propylitic and phyllic), and a late argillic episode. Silver mineralization primarily belongs to the late paragenetic sequence III. Freibergite is the dominant and most important Ag-mineral in the deposit. Detailed ore mineralogy of Bianjiadayuan freibergite reveals evidence of chemical heterogeneity down to the microscale. Silver-rich sulfosalts in the late paragenetic sequence III are largely derived from a series of retrograde and solid-state reactions that redistribute Ag via decomposition and exsolution during cooling, illustrating that documentation of post-mineralization processes is essential for understanding silver ore formation. Sulfur and lead isotope compositions of sulfides, and comparison with those of local various geological units, indicate that the ore-forming fluids, lead, and other metals have a magmatic origin, suggesting a close genetic association between the studied Ag-Pb-Zn veins and the local granitic intrusion. Fluid cooling coupled with decreases in fO2 and fS2 are the factors inferred to have led to a decrease of silver solubility in the hydrothermal fluid, and successively promoted extensive Ag deposition.

The classification of the tetrahedrite group minerals in keeping with the current IMA-accepted nomenclature rules is discussed. Tetrahedrite isotypes are cubic, with space group symmetry I4̄3̄m. The general structural formula of minerals belonging to this group can be written as M(2)A6M(1)(B4C2)X(3)D4S(1)Y12S(2)Z, where A=Cu+, Ag+, [](vacancy), and (Ag6)4+ clusters; B=Cu+, and Ag+; C=Zn2+, Fe2+, Hg2+, Cd2+, Mn2+, Cu2+, Cu+, and Fe3+; D=Sb3+, As3+, Bi3+, and Te4+; Y=S2- and Se2-; and Z=S2-, Se2-, and []. The occurrence of both Me+ and Me2+ cations at the M(1) site, in a 4:2 atomic ratio, is a case of valency-imposed double site-occupancy. Consequently, different combinations of B and C constituents should be regarded as separate mineral species. The tetrahedrite group is divided into five different series on the basis of the A, B, D, and Y constituents, i.e., the tetrahedrite, tennantite, freibergite, hakite, and giraudite series. The nature of the dominant C constituent (the so-called \"charge-compensating constituent\") is made explicit using a hyphenated suffix between parentheses. Rozhdestvenskayaite, arsenofreibergite, and goldfieldite could be the names of three other series. Eleven minerals belonging to the tetrahedrite group are considered as valid species: argentotennantite-(Zn), argentotetrahedrite-(Fe), kenoargentotetrahedrite-(Fe), giraudite-(Zn), goldfieldite, hakite-(Hg), rozhdestvenskayaite-(Zn), tennantite-(Fe), tennantite-(Zn), tetrahedrite-(Fe), and tetrahedrite-(Zn). Furthermore, annivite is formally discredited. Minerals corresponding to different end-member compositions should be approved as new mineral species by the IMA-CNMNC following the submission of regular proposals. The nomenclature and classification system of the tetrahedrite group, approved by the IMA-CNMNC, allows the full description of the chemical variability of the tetrahedrite minerals and it is able to convey important chemical information not only to mineralogists but also to ore geologists and industry professionals.

Production of radionuclide-free copper concentrates is dependent on understanding and controlling the deportment of daughter radionuclides (RNs) produced from 238U decay, specifically 226Ra, 210Pb, and 210Po. Sulfuric acid leaching is currently employed in the Olympic Dam processing plant (South Australia) to remove U and fluorine from copper concentrates prior to smelting but does not adequately remove the aforementioned RN. Due to chemical similarities between lead and alkaline earth metals (including Ra), two sets of experiments were designed to understand solution interactions between Sr, Ba, and Pb at various conditions. Nanoscale secondary ion mass spectrometry (NanoSIMS) isotopic spatial distribution maps and laser ablation inductively coupled-plasma mass spectrometry transects were performed on laboratory-grown crystals of baryte, celestite, and anglesite which had been exposed to different solutions under different pH and reaction time conditions. Analysis of experimental products reveals three uptake mechanisms: overgrowth of nearly pure SrSO4 and PbSO4 on baryte; incorporation of minor of Pb and Ba into celestite due to diffusion; and extensive replacement of Pb by Sr (and less extensive replacement of Pb by Ba) in anglesite via coupled dissolution-reprecipitation reactions. The presence of H2SO4 either enhanced or inhibited these reactions. Kinetic modelling supports the experimental results, showing potential for extrapolating the (Sr, Ba, Pb)SO4 system to encompass RaSO4. Direct observation of grain-scale element distributions by nanoSIMS aids understanding of the controlling conditions and mechanisms of replacement that may be critical steps for Pb and Ra removal from concentrates by allowing construction of a cationic replacement scenario targeting Pb or Ra, or ideally all insoluble sulfates. Experimental results provide a foundation for further investigation of RN uptake during minerals processing, especially during acid leaching. The new evidence enhances understanding of micro- to nanoscale chemical interactions and not only aids determination of where radionuclides reside during each processing stage but also guides development of flowsheets targeting their removal.

Concentration data are reported for 18 trace elements in chalcopyrite from a suite of 53 samples from 15 different ore deposits obtained by laser-ablation inductively-coupled plasma-mass spectrometry. Chalcopyrite is demonstrated to host a wide range of trace elements including Mn, Co, Zn, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi. The concentration of some of these elements can be high (hundreds to thousands of ppm) but most are typically tens to hundreds of ppm. The ability of chalcopyrite to host trace elements generally increases in the absence of other co-crystallizing sulfides. In deposits in which the sulfide assemblage recrystallized during syn-metamorphic deformation, the concentrations of Sn and Ga in chalcopyrite will generally increase in the presence of co-recrystallizing sphalerite and/or galena, suggesting that chalcopyrite is the preferred host at higher temperatures and/or pressures. Trace-element concentrations in chalcopyrite typically show little variation at the sample scale, yet there is potential for significant variation between samples from any individual deposit. The Zn:Cd ratio in chalcopyrite shows some evidence of a systematic variation across the dataset, which depends, at least in part, on temperature of crystallization. Under constant physiochemical conditions the Cd:Zn ratios in co-crystallizing chalcopyrite and sphalerite are typically approximately equal. Any distinct difference in the Cd:Zn ratios in the two minerals, and/or a non-constant Cd:Zn ratio in chalcopyrite, may be an indication of varying physiochemical conditions during crystallization. Chalcopyrite is generally a poor host for most elements considered harmful or unwanted in the smelting of Cu, suggesting it is rarely a significant contributor to the overall content of such elements in copper concentrates. The exceptions are Se and Hg which may be sufficiently enriched in chalcopyrite to exceed statutory limits and thus incur monetary penalties from a smelter.

Pyrite, the most common sulfide mineral, is a ubiquitous component of many hydrothermal gold deposits. Geochemical patterns within the refractory pyrite structure represent a valuable repository of information that can help constrain the sources of ore-forming materials, and the evolution of ore-forming processes over time. However, there are still a lot of debates on the mechanisms of physico-chemical processes in ore-forming fluid controlling trace element and sulfur isotope distributions in pyrite during growth. In our manuscript, we use cutting-edge complementary microanalytical methods to understand the origin and evolution of zoned gold-bearing pyrite in samples from the largest gold deposit in the Ailaoshan gold belt, SW China, Zhenyuan (exceeding 100t Au, average grade: 5.3 g/t). Pyrite, arsenopyrite, chalcopyrite, and stibnite are the most abundant sulfide minerals in most orebodies. Of these, pyrite is dominant and is also the most important host for gold. Two types of pyrite can be clearly distinguished: framboidal pyrite and hydrothermal pyrite. Gold is most commonly hosted by hydrothermal pyrite. Framboidal pyrite, mainly hosted by carbonaceous slate, hosts negligible Au, and features low δ 34 S values ranging from − 35.0 (± 0.9) to − 25.6 (± 1.0)‰. Hydrothermal pyrite is characterized by complex intra-grain zoned textures with alternating As-rich and As-poor bands readily recognizable on backscattered electron images. Scanning electron microscopy and trace-element analyses show that both visible and invisible gold occur only in the As-rich bands. Compared to the As-poor bands (72.1% of Au concentration data < 1.96 ppm, n  = 43), the As-rich bands are characterized by far higher concentrations of Au (up to 1420 ppm), Cu, Ag, Sb, and Tl, but lower concentrations of Co and Ni. In-situ sulfur isotope analysis indicates that the δ 34 S values of As-rich zones range from − 7.3 (± 0.6) to 2.9 (± 0.6)‰ and are similar to those of As-poor zones (from − 6.9 (± 0.7) to 2.8 (± 0.6)‰), but distinct from the framboidal pyrite. Combined with published fluid inclusion data and a probable age for the magmatic event associated with mineralization, these data suggest that magmatic–hydrothermal fluids contributed most ore-forming materials and that periodic boiling led to formation of the rhythmic As-rich and As-poor bands in pyrite. Our data for pyrite constrain the evolution of ore-forming processes and provide new insights into the formation of zoned pyrite, with the conclusions having broad implications for analogous hydrothermal gold deposits worldwide.

Sphalerite is a common sulphide and is the dominant ore mineral in Zn-Pb sulphide deposits. Precise determination of minor and trace element concentrations in sulphides, including sphalerite, by Laser-Ablation Inductively-Coupled-Plasma Mass-Spectrometry (LA-ICP-MS) is a potentially valuable petrogenetic tool. In this study, LA-ICP-MS is used to analyse 19 sphalerite samples from metamorphosed, sphalerite-bearing volcanic-associated and sedimentary exhalative massive sulphide deposits in Norway and Australia. The distributions of Mn, Fe, Co, Cu, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi are addressed with emphasis on how concentrations of these elements vary with metamorphic grade of the deposit and the extent of sulphide recrystallization. Results show that the concentrations of a group of trace elements which are believed to be present in sphalerite as micro- to nano-scale inclusions (Pb, Bi, and to some degree Cu and Ag) diminish with increasing metamorphic grade. This is interpreted as due to release of these elements during sphalerite recrystallization and subsequent remobilization to form discrete minerals elsewhere. The concentrations of lattice-bound elements (Mn, Fe, Cd, In and Hg) show no correlation with metamorphic grade. Primary metal sources, physico-chemical conditions during initial deposition, and element partitioning between sphalerite and co-existing sulphides are dominant in defining the concentrations of these elements and they appear to be readily re-incorporated into recrystallized sphalerite, offering potential insights into ore genesis. Given that sphalerite accommodates a variety of trace elements that can be precisely determined by contemporary microanalytical techniques, the mineral has considerable potential as a geothermometer, providing that element partitioning between sphalerite and coexisting minerals (galena, chalcopyrite etc.) can be quantified in samples for which the crystallization temperature can be independently constrained.